WO2006047913A1 - Matière composite de polyoléfines et procédé servant à produire celle-ci - Google Patents

Matière composite de polyoléfines et procédé servant à produire celle-ci Download PDF

Info

Publication number
WO2006047913A1
WO2006047913A1 PCT/CN2004/001383 CN2004001383W WO2006047913A1 WO 2006047913 A1 WO2006047913 A1 WO 2006047913A1 CN 2004001383 W CN2004001383 W CN 2004001383W WO 2006047913 A1 WO2006047913 A1 WO 2006047913A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
polymerization
zieglar
carbon atoms
propylene
Prior art date
Application number
PCT/CN2004/001383
Other languages
English (en)
Chinese (zh)
Inventor
Jinyong Dong
Jiguang Liu
Zhichao Han
Dujin Wang
Original Assignee
Institute Of Chemistry, Chinese Academy Of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute Of Chemistry, Chinese Academy Of Sciences filed Critical Institute Of Chemistry, Chinese Academy Of Sciences
Priority to EP04802406A priority Critical patent/EP1810991B8/fr
Priority to US11/718,256 priority patent/US20090062466A1/en
Publication of WO2006047913A1 publication Critical patent/WO2006047913A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/05—Transitioning, i.e. transition from one catalyst to another with use of a deactivating agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the invention belongs to the field of preparing polyolefin alloys, in particular to controlling the stepwise action of two kinds of catalytic components in the composite catalyst in the olefin polymerization reaction, thereby obtaining a polyolefin composite material having both good morphology and composition and adjustable properties.
  • the method of mixing different polymer materials to form a polymer composite allows the material to simultaneously obtain the advantages of two or more polymers, and can effectively improve the properties of the material.
  • a polymer composite also called a polymer alloy
  • the mechanical blending method is difficult to fully mix the polymer, especially for non-polar polyolefin materials, which is difficult to mix.
  • the method of synthesizing an alloy in situ is to directly synthesize another polymer or polymers on the surface or inside of a polymer particle, thereby achieving in-situ blending of different polymers.
  • the second polymer is in the interior of the first polymer particle, not only can a very uniform polymer composite be obtained, but also a polymer which is inherently incompatible can be uniformly mixed, which is impossible to mechanically blend. Arrived. At present, the industrialization of polyolefin alloys represented by reactor particle synthesis technology (RGT) has been highly valued.
  • RGT reactor particle synthesis technology
  • Spheripol technology is one of the first industrialized RGT technologies.
  • the polypropylene particles enter a gas phase reaction vessel, and a copolymerization reaction of ethylene and propylene is carried out inside the polypropylene particles by using an active catalyst.
  • an active catalyst Thereby a polyolefin material having high impact resistance is obtained.
  • Spherilene technology is similar to Spheripol technology and is mainly used to produce vinyl alloys.
  • the Interloy process is to first synthesize polyolefin particles using a Ziegler-Natta catalyst, and then perform free radical graft copolymerization with a radiation source in the particles to synthesize a polar monomer copolymer in the polymer particles.
  • Hivalloy technology is a graft copolymerization of a parent monomer in a polyolefin void formed by a Ziegler-Natta catalyst after olefin polymerization. It can graft a polar monomer or even a non-olefin monomer in a polyolefin matrix.
  • the polymerization such as styrene, acrylonitrile, acrylate, etc., allows the polyolefin material to have superior properties of engineering plastics.
  • Catalloy technology maximizes the superiority of RGT. In this process, a homopolymer is formed first, and second, third, and fourth monomers are sequentially introduced for polymerization, thereby directly obtaining multiple phases and multiple types in the reactor.
  • the circulating reactor technology which is technically a major step forward in catalloy technology, marks the ideal mixing of alloys and the formation of solid solutions.
  • the above techniques are all based on the technique of a heterogeneous catalyst-Ziegler-Natta catalyst, and most of the gas phase technology is used in the second polymerization.
  • the Ziegler-Natta catalyst has poor copolymerization ability and the polymer obtained by the olefin polymerization has a wide molecular weight distribution, so that it is difficult to be widely applied to the molecular design of the polyolefin material, and it is difficult to effectively improve the performance of the alloy.
  • the metallocene catalyst used for olefin polymerization is a homogeneous catalyst developed in recent years, has a single catalytically active center, has high copolymerization ability, can copolymerize most monomers, and has a narrow molecular weight distribution and comonomer distribution. Uniform, can produce syndiotactic copolymers, etc.; thus enabling the molecular design of the polymer. Therefore, the metallocene catalyst catalyzes the polymerization of the olefin, and the properties of the polymer can be set in advance according to requirements, so that the synthesis of the polymer can be carried out more efficiently and purposefully.
  • Galli et al. Montell Laboratories, Italy, published the first method of using Ziegler-Natta catalyst and metallocene catalyst together for RGT in the Journal of Applied Polymer Science, 66, page 1831, 1996.
  • the Ziegler-Natta catalyst is first deactivated with water, and then the I ⁇ -EBTHZrCl 2 solution activated by the alkyl aluminoxane is directly added, followed by gas phase copolymerization of ethylene and propylene.
  • the method is a method for physically adsorbing a metallocene catalyst, which can only be used in a gas phase process; in the slurry process, the morphology is seriously affected by the leaching of the catalyst, and it is difficult to form an ideal composite material;
  • the method will also make it difficult to ensure uniform distribution of the catalyst, so that it is difficult to ensure that the polymer formed in the second polymerization can be uniformly mixed with the polyolefin formed in the first step, so that it is difficult to obtain an ideal polymer composite even in a gas phase process. material. Summary of the invention
  • a further object of the present invention is to provide a method for preparing a polyolefin composite material, which can ensure that the polymer formed in the second step polymerization can be uniformly mixed with the polyolefin formed in the first step in the preparation of the polyolefin composite material, Effectively improve the performance of polymer composites to obtain the desired polymer composites.
  • the present invention uses a heterogeneous Zieglar-Natta and metallocene catalyst to control the heterogeneous Zieglar-Natta catalyst to function in the first step of olefin polymerization, while the metallocene compound does not function in the polymerization. A spherical polyolefin particle is produced.
  • the heterogeneous Zieglar-Natta catalyst is substantially ineffective, and the catalytic activity of the metallocene compound is activated to play a role in ethylene homopolymerization or copolymerization; molecular design can be carried out by fully utilizing the metallocene catalyst Characteristics, molecular design according to performance requirements, due to the uniform dispersion of the metallocene compound in the first step of polymerization with the fragmentation of the heterogeneous Zieglar-Natta catalyst, in the second step of polymerization, The second component polymer will be uniformly dispersed in the polypropylene matrix to form a polyolefin composite having a uniform composition.
  • the polyolefin composite material of the present invention is composed of a propylene polymer and an ethylene copolymer obtained by copolymerizing ethylene with an alpha olefin or a diolefin, wherein the molar content of the olefin or the diolefin in the ethylene copolymer From 0% to 60%, the ethylene copolymer accounts for 3 to 80% of the total weight of the polyolefin composite.
  • the polyolefin composite material of the invention has a particle form, the ethylene copolymer has a narrow molecular weight distribution (PDI of 1 to 6), a low glass transition temperature (_80 ⁇ 0 ⁇ ), and the ethylene copolymer formed in the reaction is uniformly dispersed in the propylene polymer.
  • the polyolefin composite is formed in the particles; the amount of ⁇ :olefin or diolefin monomer in the ethylene copolymer is adjustable. Thereby, the melting point of the copolymer can be adjusted from a high degree of amorphous (no defects) to 131 °C.
  • the ⁇ -olefin is an 1-olefin having 3 to 10 carbon atoms; and the carbon-diamine copolymer has 4 to 8 carbon atoms.
  • the preparation method of the polyolefin composite material of the invention comprises the following steps:
  • the first polymer produces particulate polyolefin particles.
  • an external electron donor may be added to the reaction system to control the isotacticity of the polymer in an amount of from 0 to 100 times the amount of the Ti element added to the catalyst on a molar basis.
  • the external electron donor may be an alkoxysilane (such as diphenyldimethoxysilane, phenyltriethoxysilane or 2,2,6,6-tetramethylpiperidine, etc.) or an aromatic ester (such as benzene). Ethyl formate or methyl p-methylbenzoate, etc.).
  • an inhibitor such as a ruthenium-based aluminum compound containing 3 to 9 carbon atoms may be added to suppress the catalytic activity of the metallocene. 5% ⁇ 2°/ ⁇ The amount of the solvent is 0. 5% ⁇ 2°/. .
  • the second step of the polymerization is to directly carry out a slurry polymerization reaction to the propylene polymer in the step (1) after the first step of polymerization;
  • the liquid portion of the propylene polymerization product of the step (1) is removed, and then the reaction monomer is passed through to carry out gas phase polymerization directly.
  • the reactive monomer may be an olefin having 2 to 10 carbon atoms, a diolefin or the like.
  • the reaction temperature of the three methods is from 80 ° C to 120 ° C, preferably from 90 ° C to 100 ° C.
  • Reactivation of the metallocene catalyst in a dormant state is achieved by changing the reactive monomer and/or adding an activator or the like of 1% or more of the total weight of the catalyst.
  • an aluminum alkyl or an alkyl aluminoxane may be further added as a co-catalyst, and the molar ratio of the aluminum element to the metal element in the metallocene compound in the composite catalyst is 0 ⁇ . 16000.
  • the pressure of the reaction in the above two steps should be carried out at 1 atm to 100 atm, and the number of carbon atoms in the alkyl aluminum or alkyl aluminoxane added in the above two-step reaction is 1 to 12.
  • the composite catalyst formed by the heterogeneous Zieglar-Natta catalytic component of the present invention and the catalytic component of the metallocene compound has a spherical, porous character. It consists of two parts, namely a metallocene compound activated by an alkyl aluminum or an alkyl aluminoxane and a heterogeneous Zieglar-Natta catalyst system, wherein the number of carbon atoms in the alkyl aluminum or alkyl aluminoxane is 1 ⁇ 12.
  • the catalytic component of the activated metallocene compound is from 1% to 50% by weight based on the total weight of the composite catalyst. It is preferably 20% to 40%.
  • the heterogeneous Zieglar-Natta catalyst system is a catalyst having a spherical morphology containing titanium tetrachloride or titanium trichloride and an internal electron donor supported on magnesium chloride.
  • the percentage of each component in the heterogeneous Zieglar-Natta catalytic system is: magnesium content is 10% ⁇ 30%, titanium content is: 2% ⁇ 6%, chlorine content is 50% ⁇ 70%, internal electron donor The content is: 3% to 25%.
  • the percentage of each major element in the heterogeneous Zieglar-Natta catalytic system is preferably: magnesium content is 15% to 22%, titanium content is: 3% to 4%, chlorine content is 55% to 65%, internal electron supply The body is 10% ⁇ 20%.
  • the internal electron donor in the heterogeneous Zieglar-Natta catalytic system of the present invention is: diisobutyl phthalate, dibutyl phthalate, diethyl succinate, decane or the following Compound: Wherein, it is methyl or ethyl; R 3 is
  • R 5 , , R 7 and R 8 are 1 to 8 carbon atoms
  • the molar ratio of the metal element in the metallocene compound to the aluminum element in the mercapto aluminum or the alkyl aluminoxane is 1: 50 ⁇ 1: 2000 ⁇ alkyl aluminum or mercapto aluminoxane
  • the number of carbon atoms in the range is 1 to 12.
  • the metallocene compound is a compound having the following formula: R ⁇ R ⁇ MC ⁇
  • I 1 and R 2 are respectively Me 2 Si(Ind) 2 , Me 2 Si(2-Me-4-Ph-Ind) 2 , Me 2 Si(2-Me-Ind) 2 , Me(Me 3 Si) Si(2-Me-4-Ph-Ind) 2 , Me 2 Si(IndR 2 ) 2 , Et(Ind) 2 , Me 2 SiCp, MeCp, Cplnd, Cp, Ph 2 C(Cp)(Flu) , Pli 2 C (CpX2-Me 2 NFlii) or Ph2C (CpX2-MeOFlu); a thiol group of 1 to 3 carbon atoms in the formula Me 2 Si(IndR 2 ) 2 .
  • Me is CH 3
  • Ind is a fluorenyl group
  • Ph is a benzene ring
  • Et is an ethyl group
  • Cp is a cyclopentadiene
  • F i is fluorene.
  • Process for the preparation of a composite catalyst for olefin polymerization or copolymerization of the present invention mixing a mixture of an alkyl aluminum or an alkyl aluminoxane with a metallocene compound with a spherical Zieglar-Natta catalytic component, an alkyl aluminum or an alkane
  • the number of carbon atoms in the aluminoxane is from 1 to 12.
  • each gram of Zieglar-Natta catalytic component is mixed with I x 10 6 mol to 5.6 x 10 4 mol of the activated metallocene compound, preferably 2 x 1 (T 5 mol to 1.0 x 10 4 mol.
  • the mixing temperature is 0 ° C.
  • the mixture is stirred at 80 ° C, then filtered, and thoroughly washed with an alkane or aromatic hydrocarbon solvent of 5 to 10 carbon atoms to obtain a composite catalyst.
  • the preparation process is carried out in an inert gas.
  • the inert gas includes nitrogen, argon, helium.
  • the aluminum alkyl or mercaptoaluminoxane is dissolved in a solvent and then mixed with a metallocene compound in which the number of carbon atoms in the alkyl aluminum or mercaptoaluminoxane is from 1 to 12.
  • the molar ratio of the metal element in the metallocene compound to the aluminum element in the aluminum alkyl or alkyl aluminoxane is 1:50 ⁇ 1:2000, preferably 1:80 ⁇ 1:300; the temperature is 0 °C ⁇ 90 °C Preferably, it is stirred at 0 ° C to 50 ° C.
  • the solvent described therein is an anthracene hydrocarbon or an aromatic hydrocarbon solvent of 5 to 10 carbon atoms.
  • the preparation process is carried out in an inert gas.
  • the spherical Zieglar-Natta catalyst is prepared, for example, according to the method disclosed in the literature: CN1110281A, CN1047302A, CN1091748A or US4399054 or prepared as follows: a spherical alcoholic MgCl 2 carrier having a molar ratio of alcohol to MgCl 2 of 1:1 to 4:1 (Alcohol can be an alcohol containing 2 to 4 carbon atoms) into a preparation bottle, -20 ° C ⁇ 1 (TC, preferably -20 ⁇ ⁇ 0 ⁇ according to the amount of 5 m per gram of carrier!
  • ⁇ 50 ml of titanium compound Add TiCl 4 or TiCl 3 , preferably 10 m! ⁇ 50 ml per gram of carrier titanium compound. Stir and gradually increase the temperature. When it reaches 80 ° C or higher, add the internal electron donor, then continue to raise the temperature to above 110 ° C, stir. Filter, add 5m! ⁇ 50ml of TiCl 4 or TiCl 3 , stir at 100 ° C ⁇ 150 ° C, and filter. It can be washed well with terpene hydrocarbons (pentane, hexane, hydrazine, etc.) without washing.
  • terpene hydrocarbons penentane, hexane, hydrazine, etc.
  • the present invention uses a heterogeneous Zieglar-Natta catalytic component and a metallocene compound component composite catalyst to control the heterogeneous Zieglar-Natta catalyst to function in the first step of olefin polymerization, and the metallocene compound It does not function in the polymerization to form spherical polyolefin particles.
  • the heterogeneous Zieglar-Natta catalyst is substantially ineffective, and the catalytic activity of the metallocene compound is activated to play a role in ethylene homopolymerization or copolymerization; thus, the heterogeneous Zieglar can be fully utilized.
  • the characteristics of the -Natta catalyst give a polymer with good morphology, and can fully utilize the characteristics of molecular design of the metallocene catalyst.
  • the molecular design is carried out according to the performance requirements, and the second generation of the polypropylene particles generated in the first polymerization reaction is second. Or a third olefin homopolymer or copolymer to purposefully adjust the properties of the polymer alloy.
  • the resulting second component polymer will be uniformly dispersed in the polypropylene matrix to form a polyolefin composition having a uniform composition.
  • the practice of the present invention will result in a series of polyolefin alloy particles having good morphology, adjustable composition, and uniform mixing of different components.
  • the above activated metallocene compound was mixed with 2.8 g of the heterogeneous Zieglar-Natta catalytic component under a nitrogen atmosphere, incubated at 0 ° C, stirred for 24 hours, filtered, and washed 6-8 times each with 50 ml of toluene and hexane.
  • the composite catalyst A was obtained by vacuum drying. The composition is shown in Table 1.
  • TMA trimethylaluminum
  • TIBA triisobutylaluminum
  • the above metallocene compound solution is mixed with 2g of CS-2 heterogeneous Zieglar-Natta catalytic component (Liaoning Xiangyang Kehua Group) under nitrogen atmosphere, kept at 40 ° C, stirred for 5 hours, filtered, and each time with 30 ml of sunflower The mixture was washed 6 times, washed once with 30 ml of pentane, and dried to obtain a composite catalyst D.
  • the composition is shown in Table 1.
  • the above heterogeneous metallocene compound solution was mixed with 2 g of the heterogeneous Zieglar-Natta catalytic component under a nitrogen atmosphere, kept at 60 Torr, mechanically stirred for 4 hours, vacuum-filtered, washed 6 times with toluene, and vacuum-dried to obtain a composite catalyst E.
  • the composition is shown in Table 1.
  • a solid compound of 0.5 mmol of Cp 2 ZrCl 2 was placed in a two-necked argon-filled flask, followed by the addition of 40 ml of a 4 M solution of MAO in xylene, and stirred at 0 ° C for 48 hours.
  • the above metallocene compound solution was mixed with 2 g of CS-3 heterogeneous Zieglar-Natta catalyst (Liaoning Xiangyang Kehua Group) under a nitrogen atmosphere, kept at 80 ° C, mechanically stirred for 0.5 hours, vacuum filtered, washed with xylene 30 ml. After 6 passes and washing with 30 ml of amylose, the mixture was vacuum dried to obtain a composite catalyst F.
  • the composition is shown in Table 1. Table 1 ⁇
  • catalyst F 0. 05g of catalyst F, added to a 500ml reactor, adding 3ml of styrene, 150ml of heptane, 2ml of 4M TEA in heptane solution, 60 ° C, 6 atmospheres, propylene, 3 (3 minutes). 6 ml of terpene, ethylene was introduced at 6 atm, and the temperature was raised to 90 Torr for 10 minutes.
  • Example 8 Geng, TMA propylene; 40. C, latm; 280 40 0 131 156 pentane TEA ethylene 120°C, 6atm
  • Example 10 Geng, TEA, propylene, p-methylstyrene; 60 ° C, latm; 180 40 0- 130 158 Nude Ethylene 120 ° C, latm
  • Example 11 Heptane TEA Propylene, styrene; 80 ° C, latm; 260 60 8 121 156 Ethylene, propylene 100. C, 5atm
  • Example 12 Toluene, MAO; Propylene, Styrene; C, latm; 160 40 6 118 158 Geng Teng TIBA Ethylene, propylene 95 °C, latm
  • Example 13 Sacrificial TEA Propylene, styrene; 40 ° C, latm; 180 10 10 118 156 Ethylene, TM 120 ° C, 1 atm
  • Example 15 Grafting TEA Propylene, styrene; 60 ° C, 6 atm; 600 3 60 152 Ethylene, octene 90. C, 6atm
  • Example 17 ⁇ ⁇ TEA propylene, styrene; 60. C, 6atm; 620 70 40 155 Ethylene, C 90 ° C, 6 atm
  • the monomer content is the percentage of other olefin monomers copolymerized with ethylene in addition to ethylene in the copolymer.
  • the PE and PP contents of the polymer are calculated from the amount consumed in the reaction. Italic is the monomer of the second step reaction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne le domaine de la préparation d'alliages de polyoléfines, en particulier l'obtention d'une matière composite de polyoléfines ayant une bonne morphologie, une composition ajustable et des propriétés ajustables en réglant le catalyseur composite constitué d'un catalyseur de Ziegler-Natta et d'un catalyseur métallocène pour qu'il fonctionne par paliers. La matière est constituée d'un polymère du propylène et d'un copolymère de l'éthylène ; ledit copolymère de l'éthylène est obtenu en copolymérisant de l'éthylène avec une alpha-oléfine ou un diène, la teneur molaire de l'alpha-oléfine ou du diène dans le copolymère de l'éthylène allant de 0 % à 60 % ; le copolymère de l'éthylène constitue de 3 à 80 % en poids de la matière composite de polyoléfines ; ladite matière composite de polyoléfines a une morphologie particulaire ; la distribution du poids moléculaire du copolymère de l'éthylène va de 1 à 6, la température de transition vitreuse va de -80 à 0°C ; le copolymère de l'éthylène produit dans la réaction est uniformément dispersé dans la particule de polymère du propylène pour former la matière composite de polyoléfines.
PCT/CN2004/001383 2004-11-05 2004-11-30 Matière composite de polyoléfines et procédé servant à produire celle-ci WO2006047913A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP04802406A EP1810991B8 (fr) 2004-11-05 2004-11-30 Procédé servant à produire une matière composite de polyoléfines
US11/718,256 US20090062466A1 (en) 2004-11-05 2004-11-30 Polyolefin Composite Material And Method For Producing The Same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2004100097535A CN1328310C (zh) 2004-11-05 2004-11-05 聚烯烃复合材料及其制备方法
CN200410009753.5 2004-11-05

Publications (1)

Publication Number Publication Date
WO2006047913A1 true WO2006047913A1 (fr) 2006-05-11

Family

ID=36318871

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2004/001383 WO2006047913A1 (fr) 2004-11-05 2004-11-30 Matière composite de polyoléfines et procédé servant à produire celle-ci

Country Status (4)

Country Link
US (1) US20090062466A1 (fr)
EP (1) EP1810991B8 (fr)
CN (1) CN1328310C (fr)
WO (1) WO2006047913A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2003150A1 (fr) * 2007-06-13 2008-12-17 Petrochina Company Limited Procédé de préparation d'alliage de polyoléfine
US20080312390A1 (en) * 2007-06-14 2008-12-18 Petrochina Company Limited Process for preparation of polyolefin alloy
CN101891850B (zh) * 2009-05-19 2012-04-25 中国科学院化学研究所 聚丙烯组合物的制备方法及聚丙烯组合物
EP2383298A1 (fr) 2010-04-30 2011-11-02 Ineos Europe Limited Procédé de polymérisation
EP2383301A1 (fr) * 2010-04-30 2011-11-02 Ineos Europe Limited Procédé de polymérisation
CN101906179B (zh) * 2010-07-23 2012-10-17 北京化工大学 超高分子量聚烯烃催化剂的制备方法和应用
CN102174225A (zh) * 2011-01-28 2011-09-07 中国科学院化学研究所 一种多相共聚聚丙烯釜内合金及其制备方法
CN102504058B (zh) * 2011-11-10 2014-04-02 上海化工研究院 用于生产宽分子量分布聚乙烯的复合催化剂及制法和应用
CN102838701B (zh) * 2012-09-04 2014-12-10 中国科学院化学研究所 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金
US10723824B2 (en) 2014-02-07 2020-07-28 Eastman Chemical Company Adhesives comprising amorphous propylene-ethylene copolymers
US10308740B2 (en) 2014-02-07 2019-06-04 Eastman Chemical Company Amorphous propylene-ethylene copolymers
US10647795B2 (en) 2014-02-07 2020-05-12 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US10696765B2 (en) 2014-02-07 2020-06-30 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
US9382351B2 (en) 2014-02-07 2016-07-05 Eastman Chemical Company Amorphous propylene-ethylene copolymers
US11267916B2 (en) 2014-02-07 2022-03-08 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
CN105199024B (zh) * 2014-06-24 2018-01-23 中国石油化工股份有限公司 一种用于乙烯聚合的催化剂组分、催化剂及其制备方法
CN110066365B (zh) * 2018-01-22 2021-11-16 中国石油化工股份有限公司 一种功能化聚乙烯的制备方法
CN110283281A (zh) * 2019-06-26 2019-09-27 深圳聚石新材料科技有限公司 一种超高分子量聚乙烯和聚丙烯原位共混物的制备方法
CN115958853B (zh) * 2022-12-30 2023-09-22 无锡海达光能股份有限公司 一种用于光伏瓦片的层压玻璃

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
CN1250058A (zh) * 1998-10-06 2000-04-12 中国石油化工集团公司 合成宽或双峰分子量分布的聚烯烃的催化剂及制备方法
EP0586168B1 (fr) * 1992-09-04 2000-07-05 BP Chemicals Limited Compositions de catalyseurs et procédé de préparation de polyoléfines
CN1292389A (zh) * 1999-06-23 2001-04-25 中国石油兰州化学工业公司 一种烯烃聚合用复配型催化剂
EP1246849A1 (fr) * 1999-12-28 2002-10-09 Union Carbide Chemicals & Plastics Technology Corporation Catalyseurs mixtes ziegler/metallocene utilises pour produire des polyolefines a deux modes

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1098272B (it) * 1978-08-22 1985-09-07 Montedison Spa Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine
IT1270125B (it) * 1994-10-05 1997-04-28 Spherilene Srl Processo per la ( co) polimerizzazione di olefine
TW314536B (fr) * 1995-03-23 1997-09-01 Sumitomo Bakelite Co
IT1275573B (it) * 1995-07-20 1997-08-07 Spherilene Spa Processo ed apparecchiatura per la pomimerizzazione in fase gas delle alfa-olefine
CN1113900C (zh) * 1996-06-17 2003-07-09 埃克森美孚化学专利公司 用于烯烃聚合的混合过渡金属催化剂体系及用其聚合烯属不饱和单体的方法
US6160064A (en) * 1997-06-14 2000-12-12 The Board Of Trustees Of The Leland Stanford Junior University Ethylene enhancement of processes for synthesis of high melting theromoplastic elastomeric α-olefin polymers (PRE/EPE effects)
KR20010052195A (ko) * 1998-03-04 2001-06-25 엑손 케미칼 패턴츠 인코포레이티드 폴리올레핀 중합체 분산액을 제조하기 위한 생성물 및 방법
AU1987600A (en) * 1998-12-16 2000-07-03 Borealis Technology Oy Multistep process for preparing polyolefins having high melt strength
US6653254B1 (en) * 1999-02-22 2003-11-25 Fina Technology, Inc Ziegler-Natta catalyst with metallocene for olefin polymerization
US6479600B2 (en) * 2001-01-08 2002-11-12 The Penn State Research Foundation Polyolefin containing a terminal phenyl or substituted phenyl group and process for preparing same
WO2002060957A2 (fr) * 2001-01-16 2002-08-08 Exxonmobil Chemical Patents Inc. Procede de polymerisation au moyen de compositions de catalyse melangees
US7199195B2 (en) * 2001-05-07 2007-04-03 Exxonmobil Chemical Patents Inc. Polyethylene resins
WO2003008496A1 (fr) * 2001-07-17 2003-01-30 Basell Polyolefine Gmbh Procede multi-etape de (co)polymerisation d'olefines
WO2003047752A1 (fr) * 2001-11-30 2003-06-12 Exxonmobil Chemical Patents Inc. Procede de fabrication de catalyseurs mixtes ziegler-natta/metallocene
EP1380601B1 (fr) * 2002-07-12 2005-05-25 Saudi Basic Industries Corporation Catalyseur de polymerisation ziegler - metallocene supporte et polymerisation d'olefines
US6730751B2 (en) * 2002-07-16 2004-05-04 Fina Technology, Inc. Polymerization of polyethylene having high molecular weight
US6897269B2 (en) * 2002-12-27 2005-05-24 Univation Technologies, Llc Processes for transitioning between Ziegler-Natta and alumoxane-based single-site polymerization catalysts
US6858684B2 (en) * 2002-12-30 2005-02-22 Univation Technologies, Llc Processes for transitioning between various polymerization catalysts
US7172987B2 (en) * 2002-12-31 2007-02-06 Univation Technologies, Llc Bimetallic catalyst, method of polymerization and bimodal polyolefins therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
EP0586168B1 (fr) * 1992-09-04 2000-07-05 BP Chemicals Limited Compositions de catalyseurs et procédé de préparation de polyoléfines
CN1250058A (zh) * 1998-10-06 2000-04-12 中国石油化工集团公司 合成宽或双峰分子量分布的聚烯烃的催化剂及制备方法
CN1292389A (zh) * 1999-06-23 2001-04-25 中国石油兰州化学工业公司 一种烯烃聚合用复配型催化剂
EP1246849A1 (fr) * 1999-12-28 2002-10-09 Union Carbide Chemicals & Plastics Technology Corporation Catalyseurs mixtes ziegler/metallocene utilises pour produire des polyolefines a deux modes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1810991A4 *

Also Published As

Publication number Publication date
EP1810991B8 (fr) 2012-10-24
US20090062466A1 (en) 2009-03-05
EP1810991A1 (fr) 2007-07-25
EP1810991B1 (fr) 2012-05-23
EP1810991A4 (fr) 2008-04-02
CN1328310C (zh) 2007-07-25
CN1769337A (zh) 2006-05-10

Similar Documents

Publication Publication Date Title
WO2006047913A1 (fr) Matière composite de polyoléfines et procédé servant à produire celle-ci
JPH09506391A (ja) オレフィンの（共）重合法
JP2000095811A (ja) ポリエチレン又はポリプロピレンの製造方法
JP2010513651A (ja) オレフィンを重合するためのポリマー担持型メタロセン触媒組成物
JP2007533786A (ja) メタロセン触媒系を使用した重合方法
WO2013075643A1 (fr) Catalyseur de polymérisation d'oléfines, procédé de préparation, et application associée
WO2014036678A1 (fr) Système de copolymérisation à plusieurs phases de propylène, processus de polymérisation et alliage interne de cuve de polypropylène
WO2014117307A1 (fr) Catalyseur de polymérisation d'oléfines, préparation et application associées
CA2425588C (fr) Procede de preparation d'un systeme de catalyseur et son utilisation dans un procede de polymerisation
CN111019023B (zh) 烯烃聚合用催化剂及其制备方法、烯烃聚合用催化剂组合物及其应用
WO2002026838A1 (fr) Catalyseur supporte sur gel de silice se pretant a la polymerisation ou a la copolymerisation ethylenique
JPH07268016A (ja) 触媒成分の溶液をプレポリマーに含浸して得られるオレフィン重合触媒成分と、この触媒成分から得られるプレポリマー
EP2003150A1 (fr) Procédé de préparation d'alliage de polyoléfine
JP2002532582A (ja) 触媒改質剤及びオレフィンの重合におけるそれらの使用
WO2003099884A1 (fr) Terpolymeres de propylene et leur procede de polymerisation
JPH1053605A (ja) 反応遅延剤を添加するｃ２−ｃ１２アルケンポリマーの製造方法
US20080312390A1 (en) Process for preparation of polyolefin alloy
US10808052B2 (en) Spherical supported transition metal catalyst
CN100471881C (zh) 一种负载型茂金属催化剂的制备方法
JP7445722B2 (ja) オレフィン重合用触媒の調製方法
JP3496955B2 (ja) オレフィン重合用固体触媒成分の製造方法
CN114008084B (zh) 生产茂金属负载型催化剂的方法和茂金属负载型催化剂
JP3416350B2 (ja) ビニル化合物重合用触媒並びにその使用
WO2011057468A1 (fr) Catalyseur non-métallocène supporté, son procédé de préparation et son application
CN101891919A (zh) 一种聚丙烯组合物的制备方法及聚丙烯组合物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 11718256

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2004802406

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2004802406

Country of ref document: EP